Liquid phase refining of petroleum hydrocarbon products



Patented Sept. 14, 1948 LIQUID PHASE name or PETROLEUM nrlmocimnon rnonucrs Ferdinand W. Breth and Anthony Kinsel, Pe-

trolia. Pa., a'ssignors to L. Sonneborn Sons, Inc., a corporation of Delaware No Drawing. Application March 8, 1946, Serial No. 653,128

13 Claims. 1

This invention relates to new and useful improvements in the liquid phase refining of petroleum hydrocarbon products.

In conventional petroleum hydrocarbon refining, the products are charged in liquid condition onto filters of a suitable petroleum refining adsorbent and are permitted to percolate therethrough. If the petroleum hydrocarbons are normally liquid as, for example, overhead distillates or residual stocks, they are filtered as such or in solution in volatile hydrocarbon solvents. If the same, however. are normally solid, as, for example, waxes, paraflin or petrolatum, they are charged onto the filter for percolation in substantially molten condition. A variety of filter materials are conventionally used as petroleum refining adsorbents, such as activated carbon, bone black, fullers earth, bauxite, magnesite,silica and silica gels, and alumina. These petroleum refining adsorbents are usually substantially granular materials of about 10 to 100 and preferably 30 to 60 mesh. Some of them are specially treated or activated, as is well understood in the art, to increase their refining efiiciency. The filtrate emerging from the bottom of the column of adsorbent material is usually segregated into fractions of step-wise graduated purity. The fraction first emerging from the filter is the most highly refined or purified while succeeding fractions possess progressively decreasing degrees of purity commensurate with the gradual exhaustion of the adsorbent. The efliciency of the refining procedure is measured by the total yield of improved or refined prodnot from a given quantity of raw stock or by the yield of a given fraction of the refined product defined by predetermined grades or tests of purity as to color, odor. haze, cast, fluorescence, or relative freedom from impurities such as sulfur or carbon residue yielding substances.

One object of our invention comprises inter alia. an improved method for materially increasing the yields of desired fractions refined petroleum hydrocarbons of predetermined grade or degree of purity from a given raw stock.

This and other objects of the invention will be apparent from the following description.

The improvement in petroleum hydrocarbon refining in accordance with the invention essentially comprisessublecting a petroleum hydrocarbon refining adsorbent to vibrations for a period sufilcient to obtain an over-all volume reduction of said adsorbent of at least 5% and thereafter filtering a petroleum hydrocarbon in 2 liquid phase through the said adsorbent thus vibrated.

In the practical application of our invention, a suitable granular adsorbent, preferably of about 30 to mesh, as it is normally used for pctroleum hydrocarbon percolation refining, such as activated carbon. bone black, fullers earth, bauxite and preferably activated bauxite, magnesite, silica or silica gel, alumina and preferably activated alumina, is subjected while substantially dry (1. e., substantially unwetted by petroleum hydrocarbon) to prolonged vibrations for a period sufiicient to reduce the volume of the adsorbent by approximately at least 2% and preferably approximately at least 10 to 15%, whereupon the petroleum hydrocarbon is percolated through the thusly vibrated adsorbent in substantially liquid condition. Depending upon the material used. optimum volume reduction through vibration may be as high as 40% or higher.

The petroleum hydrocarbon adsorbent may be subjected in accordance with the invention to prolonged vibration in any convenient manner, and preferably by the use of a suitable vibrating mechanism. The rate of vibration may be varied throughout a relatively wide range. A suitable vibrating device may be one actuated by an appropriate mechanism, such as an electrical, hydraulic, or pneumatic mechanism, in which vibrations of for instance an order of magnitude of about 2000 to 5000 vibrations per minute are produced by the use of appropriate means, as is *well understood in the art of vibrating devices. Vibrations should be continuous for at least several minutes at a time. For best results, it is of advantage to continue the vibrations to which petroleum "refining adsorbent is subjected for a period sufilcient to produce an over-all reduction of volume of the filter material of approximately at least 2% and preferably at least 10 to 15%. As a rule no material increase in the effectiveness of the vibrated filter material is obtained by continuing the vibrations beyond the point of optimum volume reduction. reduction in accordance with the invention serves as an outward measure coinciding with optimum efiiciency imparted to the filter material by the vibrations.

The filter material may be vibrated until the desired volume reduction is obtained prior to the delivery of hydrocarbon material to the filter top. Alternatively vibration may be commenced or continued simultaneously with the delivery of hydrocarbon material to the filter top.

Volume 2,449,oc1 v 3 4 A suitable vibrator useful in accordance with Total yield of refined fraction of predetermined the invention may be for instance one of the purity of aLovlbond color of 4R inch cell) and electrically, solenoid actuated types. The vlbraa carbon test of 0.8% was 1200 gallons per ton. tor or vibrating unit thereof is preferably at- EXAMPLE Iv tached to the outside of a filter unit or column, 5

and when set in motion transmits vibrations The same filter material using an identical filthrough the walls of the filter unit or column ter column as described in Example III was to the petroleum hydrocarbon adsorbent conused. The filter charged with the adsorbent to tained therein. Alternatively, the vibrator may capacity was closed and subjected to vibration be so utilized as to transmit its vibrations to in the manner set forth in Example II. Optimum metal rods or members suspended within the reduction in over-all volume of about 10% filter filter. After the desired Volume reduction of material was obtained after approximately onefilter material and preferably a volume reduchalf hour, using the same vibrator arrangement tion approaching optimum reduction is obtained, as described in connection with Example II. The the vibrator is turned oif and the petroleum same stock as used in Example III was then perhydrocarbon is pumped in liquid condition onto colated through the vibrated fullers earth in the the top of the filter and permitted to percolate manner set forth in Example III. Total yield through. Optimum volume reduction is conof refined fraction of predetermined purity of sidered obtained when upon continued vibration a Lovibond color or 4B. (1 inch cell) was 1870 for a period of approximately fifteen minutes no gallons per ton, showing a carbon test of 0.8%. further appreciable reduction in volume is ob- EXAMPLE V served. When using a normally solid petroleum hydrocarbon of the wax, petrolatum or parafiin A mlcrllcrystalline Wax 0f the following ch rtype, the same is first converted into the liquid actensflcs was used: phase by melting and is then pumped onto the ASTM, 1: 140.150 R filter 11mm in molten In many ASTM,penetration--40 pen. at 77 F. (needle) cases improved results are achieved by the use of several or multiple vibrators on a single filter This wax was permuted m molten condition column through a 15 foot five-ton filter column filled to The f ll i g examples and tables are f capacity with 30 to 60 mesh fullers earth in the mshed by way f illustration but not of 11mm," 30 manner described in Example I. Total yield of n refined fraction haze-free and white in color was EXAMPLE I 670 gallons per ton.

A standard filter column of about 15 feet high LE VI having a capacity of about five tons of filter ma- Using the same filter and filter material as tenal charged to capacity with activated set forth in connection with Example V, the filter bauxite of 30 to 60 mesh. A raw lubricating oil material was subjected to vlbl'atlon using the stock having a Saybolt viscosity of 64 (seconds ,same vibrating a cmditims set i at R) a Lovibond color of (116 men cell) in Example II. Vibration was continued until and a carbon test of was pumped onto the 40 about 10% reduction in volume was obtained, filter and permitted to percolate through. The which was accomplished after proximately onetotal yield of the refined fraction of predeterhalf hour- The same stock used Example V mined Lovibond color of 4R (1 5 inch cell) was i if 5 g g ma er a e manner se or n xamp e 1482 gallons per ton having a carbon test of 0.7%. a Total yield of refined fraction haze free and EXAMPLEH white in color was 1350 gallons per ton. A 15 foot five-ton capacity filter column as de- EXAMPLE V11 scribed i Example I and charged to capacity with activated bauxite was used. The filter was Example V was repeated except an activated closed and the column subj acted to vibrations bauxite was used as the adsorbent in lieu of fullers for one hour by means of three i f ti u earth therein set forth. All other conditions as disposed electric vibrators operating at an avert0 stock type and capacity of filter and Procedure age frequency of 3500 vibrations per minute and were identical with those set forth in Example V. having a normal Capacity f being operated at Total yield of refined fraction haze-free and white a range of from 2400 to 4800 vibrations per minin was 700 gallons Per ute. At the end of this vibration period about EXAJLPLE VH1 10% reduction in volume of the bauxite had taken place and continued vibrations for about another Using the same filter and filter material as set forth in Example -VII the filter material was sub- 5 b igg g i 33 33; R213: 23 35 53: 2: f gg g 50 jected to vibration as set forth in connection with Example I was then percoiated through the vi- Example n untgnabout 10% m? mfvolume brated filter material, percolating being disconf i W ch was accomphs ed ter tinuedwith the exhaustion of the filter material pm mate y one hour The same stock used as evidenced by absence of improvement of the i m was then percolated through t 8 color of the filtrate compared to that of the raw vi ed filter m the manner set forth in Exam stock used. The total yield of refined fraction ple Total yield of refined fraction haze'free of predetermined purity of a Lovibond color of and white in color was 2150 gallons per 4R (1; inch cell) was 2394 gallons per ton having Exam 1x carbon test of A crude petrolatum of the following character- EXAMPLE III istics was used:

A five-ton capacity filter column of 15' height TM 125o 1 0 was charged with fullers earth of 30 to 60 mesh g gt zi' and the same lubricating oil raw stock specified in Example I was 'percolated through the filter. The petrolatum was percolated in molten condition through a fifteen-foot, five-ton filter column filled to capacity with 80 to 60 mesh fullers earth in the manner described in Example I. Total yield of refined fraction of predetermined purity of a Lovibond 2 Yellow (2 inch cell) was 312 gallons per ton.

Exlulru: X

then percolated through the vibrated filter material in the manner set forth in Example 11.

Total yield of refined fraction of predetermined purity of 2 Yellow Lcvibond (2 inch cell) was 718 gallons per ton.

about 10% reduction in volume was obtained, which was accomplished after approximately 1 hour. The same stock used in Example XIII was then percolated through the vibrated filter material in the manner set forth in Example 1.1- Total yield of white sulfur-free doctor negative product was 4040 gallons per ton.

Using instead of the bauxite or fullers earth specified in any of the foregoing examples any other conventional petroleum refining absorbent of the preferred mesh size, 1. e., between and 60 mesh, such as silica or silica gel, magnesite, clay, alumina, activated alumina or any other well known and conventionally used petroleum hydrocarbon adsorbent. improvements of gallon yield for the predetermined color ranges similar to those set forth in connection with the herein specified examples, are obtained.

The pertinent data and various results obtained as described in the above examples are set forth in the following table:

Table YieldsinGals. Tests a Stock rum- Material vibrated Emma tional Lov. Color Other llube on- Saybolt Visc 210-04- Fuller's earth 1 200 1 s70 se 4a 34 "cell b all B .t. {a it. ar a 62 --...d 0. b Microcrystalllne a, 610 1.350 102 Whit: nzs r r eef a 700 2,150 301 ----do Do. mdePetro atum 312 m 13 1? e40 550 no -....do RewKu-oeene 2,170 4,040 88 White Sulfur negative copper dish test Exam In As will be seen from the foregoing table, the

The same petrolatum specified in connection with Examples IX and X was percolated through a 30 foot two-ton filter column filled to capacity with 30 to 60 mesh activated bauxite in the manner described in Example I. Total yield of refined fraction of predetermined purity of 2 Yellow Lovibond (2 inch cell) was 340 gallons per ton.

Exam 1.: XII

Using the same filter and filter material as set forth in the preceding example, the filter material was subjected to vibration, using the same vibrating means and conditions set forth in Example II. Vibration was continued until about 10% reduction in volume was obtained, which was acc'ompllshed after approximately 1 hour. The same stock used in previous example was then percolated through the vibrated filter material in the manner set forth in Example 11. Total yield of refined fraction of predetermined purity of 2 Yellow Lovibond (2 inch cell) was 850 gallons per ton.

Exnrru XIII A raw kerosene (sulfur copper dish test black) was percolated through a 15 foot five-ton filter column filled to capacity with 30 to 60 mesh activated bauxite in the manner described in Example 1. Total yield of refined fraction of a white, sulfur-free doctor negative product was 2,170 gallons per ton.

Exam; XIV

Using the same filter and filter material as set The foregoing description is for purposes of illustration and not of limitation, and it is, therefore, our intention that the invention be limited only by the appended claims or their equivalents wherein we have endeavored to claim broadly all inherent novelty.

We claim:

1. In the method of refining petroleum hydrocarbons, the improvement which comprises subjecting a mass of particled petroleum hydrocarbonrefining mineral-adsorbent to vibration for a period sufilcient to obtain an over-all volume reduction of said mass of adsorbent of at least approximately 5% and thereafter filtering a petroleum hydrocarbon in liquid phase through the said volume reduced adsorbent thus vibrated.

2. The improvement in accordance with claim 1 in which said petroleum hydrocarbon adsorbent is vibrated until it exhibits approximately at least 10% to 15% reduction in volume.

3. The improvement in accordance with claim 1 in which said petroleum hydrocarbon adsorbent is vibrated until it exhibits optimum reduction in volume.

4. In the method of refining petroleum hydrocarbons, the improvement which comprises sub- Jecting a mass of particled petroleum hydrocarbon refining mineral adsorbent to vibrations at an order of magnitude of approximately from forth in connection with Example XIII, the filter material was subjected to vibration, using the same vibrating means and conditions set forth 2000 to 5000 vibrations. per minute for a period sufilcient to impart to said mass of adsorbent at least approximately 5% reduction in volume and in Example 11. Vibration was continued until 76 thereafter filtering a petroleum hydrocarbon in liquid phase through said volume reduced adsorbent thus vibrated.

5. The improvement in accordance with claim 4 in which said petroleum hydrocarbon adsorbent is-vibrated until it exhibits approximately at least 10% to 15% reduction in volume.

6. The improvement in accordance with claim 4 in which said petroleum hydrocarbon adsorbent is vibrated until it exhibits optimum reduction in volume.

7. In the method of refining petroleum hydrocarbons, the improvement which comprises subjecting a mass of partlcled petroleum hydrocarbon refining mineral adsorbent to vibration for a period sufficient to obtain an over-all volume reduction of said mass of adsorbent 01' at least approximately 5% and thereafter filtering a normally liquid petroleum hydrocarbon through duction of said mass 01' adsorbent of at least approximately 5% and thereaiterflltering a normally solid petroleum hydrocarbon in molten condition through the said volume reduced adsorbent thus vibrated.

10. The improvement in accordance with claim 9 in which said petroleum hydrocarbon adsorbent 8 is vibrated until it exhibits approximately at least 10% to 15% reduction in volume.

11. In the method of refining petroleum hydrocarbons the improvement which comprises sub- Jecting a mass of particled petroleum hydrocarbon refining mineral adsorbent to vibration for a period sufiicient to obtain an over-all volume reduction of said mass of adsorbent of at least 2% and thereafter filtering molten petrolatum through the said volume reduced adsorbent thus vibrated.

12. The improvement in accordance with claim 11 in which said adsorbent is vibrated until it exhibits approximately 10% to 15% reduction in volume.

13. The improvement in accordance with claim 11 in which said adsorbent is activated bauxite vibrated until it exhibits optimum reduction in volume.

FERDINAND W. BRETH. ANTHONY KINSEL.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name V Date 2,160,874 Kinsel June 6, 1939 2,206,337 Steele July 2, 1940 2,387,171 Morgan Oct. 16, 1945 2,390,917 Breth et a1. Dec. 11, 1945 2,392,915 Grosse et a1. Jan. 15, 1946 2,413,072 Brown Feb. 4, 1947 

